WO2006028021A1 - Procédé d’entraînement d’équipement de production d’énergie à pile à combustible et équipement de production d’énergie à pile à combustible - Google Patents

Procédé d’entraînement d’équipement de production d’énergie à pile à combustible et équipement de production d’énergie à pile à combustible Download PDF

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Publication number
WO2006028021A1
WO2006028021A1 PCT/JP2005/016133 JP2005016133W WO2006028021A1 WO 2006028021 A1 WO2006028021 A1 WO 2006028021A1 JP 2005016133 W JP2005016133 W JP 2005016133W WO 2006028021 A1 WO2006028021 A1 WO 2006028021A1
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WIPO (PCT)
Prior art keywords
fuel
power generation
concentration
unit
generation unit
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PCT/JP2005/016133
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English (en)
Japanese (ja)
Inventor
Go Sudo
Kenji Katori
Masahiko Tahara
Original Assignee
Sony Corporation
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Filing date
Publication date
Application filed by Sony Corporation filed Critical Sony Corporation
Priority to US11/574,791 priority Critical patent/US8241799B2/en
Priority to EP05781399A priority patent/EP1798796B1/fr
Publication of WO2006028021A1 publication Critical patent/WO2006028021A1/fr

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1009—Fuel cells with solid electrolytes with one of the reactants being liquid, solid or liquid-charged
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
    • H01M8/04089—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
    • H01M8/04186—Arrangements for control of reactant parameters, e.g. pressure or concentration of liquid-charged or electrolyte-charged reactants
    • H01M8/04194—Concentration measuring cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
    • H01M8/04201—Reactant storage and supply, e.g. means for feeding, pipes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04298—Processes for controlling fuel cells or fuel cell systems
    • H01M8/04313—Processes for controlling fuel cells or fuel cell systems characterised by the detection or assessment of variables; characterised by the detection or assessment of failure or abnormal function
    • H01M8/04537—Electric variables
    • H01M8/04544—Voltage
    • H01M8/04559—Voltage of fuel cell stacks
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04298—Processes for controlling fuel cells or fuel cell systems
    • H01M8/04694—Processes for controlling fuel cells or fuel cell systems characterised by variables to be controlled
    • H01M8/04746—Pressure; Flow
    • H01M8/04753—Pressure; Flow of fuel cell reactants
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04298—Processes for controlling fuel cells or fuel cell systems
    • H01M8/04694—Processes for controlling fuel cells or fuel cell systems characterised by variables to be controlled
    • H01M8/04791—Concentration; Density
    • H01M8/04798—Concentration; Density of fuel cell reactants
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2250/00—Fuel cells for particular applications; Specific features of fuel cell system
    • H01M2250/20—Fuel cells in motive systems, e.g. vehicle, ship, plane
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04298—Processes for controlling fuel cells or fuel cell systems
    • H01M8/04313—Processes for controlling fuel cells or fuel cell systems characterised by the detection or assessment of variables; characterised by the detection or assessment of failure or abnormal function
    • H01M8/0432—Temperature; Ambient temperature
    • H01M8/04365—Temperature; Ambient temperature of other components of a fuel cell or fuel cell stacks
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1007—Fuel cells with solid electrolytes with both reactants being gaseous or vaporised
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1009—Fuel cells with solid electrolytes with one of the reactants being liquid, solid or liquid-charged
    • H01M8/1011—Direct alcohol fuel cells [DAFC], e.g. direct methanol fuel cells [DMFC]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T90/00—Enabling technologies or technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02T90/40—Application of hydrogen technology to transportation, e.g. using fuel cells

Definitions

  • the present invention relates to a method for operating a fuel cell power generation device and a fuel cell power generation device operated by the operation method.
  • a fuel cell is a power generation element that generates power by electrochemically reacting a fuel such as hydrogen or methanol with an oxidant gas such as oxygen.
  • Fuel cells are attracting attention as power generation elements that do not pollute the environment because the product generated by power generation is water. For example, attempts have been made to use them as drive power sources for driving automobiles. And
  • Fuel cells are classified into various types according to differences in electrolytes, etc., and representative ones include fuel cells using a solid polymer electrolyte as an electrolyte.
  • Solid polymer electrolyte fuel cells can be manufactured at low cost, and can be easily reduced in size, thickness, and weight, and have high output density in terms of battery performance. It is hope.
  • this solid polymer electrolyte fuel cell has been developed by reforming methanol and natural gas to produce hydrogen.
  • direct methanol fuel cells DMFCs
  • DMFCs direct methanol fuel cells
  • the DMFC has a power generation cell in which an electrolyte such as a solid polymer electrolyte is sandwiched between a force sword and an anode.
  • an electrolyte such as a solid polymer electrolyte
  • a reaction of CH OH + H 0 ⁇ CO + 6H + + 6e— occurs between the methanol and water on the anode surface.
  • a methanol aqueous solution that is mixed with high-concentration methanol and water generated by a power sword by power generation so as to have an appropriate concentration in the fuel cell power generation apparatus is prepared.
  • concentration detection a concentration sensor or a sensor cell using a capacitance method, an electrochemical oxidation method, an ultrasonic method, or a specific gravity method is used.
  • Japanese Patent Laid-Open No. 2003-22830 does not use a sensor for concentration detection, but performs a predetermined calculation using output current and operating time as parameters to detect the concentration of aqueous methanol solution. Then, the methanol aqueous solution is supplied to the fuel cell at the optimum fuel flow rate from the calculated concentration. In other words, the optimum operation of the fuel cell is performed at a flow rate that is not the concentration of the methanol aqueous solution, and fine control of the flow rate is required. Further, as described above, the output of the fuel cell tends to change with time, and the degree of change with time varies depending on the history of the apparatus, so that an error may occur in the calculated concentration. In addition, complex calculations must be performed to calculate the concentration.
  • the present invention supplies diluted fuel having an optimal concentration to the power generation unit without performing absolute concentration measurement of a sensor or the like, so that the load or the fuel cell power generator It is an object of the present invention to provide a method of operating a fuel cell power generator that adjusts the concentration of diluted fuel so as to maximize the output characteristics and power generation efficiency characteristics according to the installation conditions. Another object of the present invention is to provide a fuel cell power generator that is supplied with diluted fuel adjusted to an optimum concentration that can maximize output characteristics and power generation efficiency characteristics by this operation method.
  • the operation method of the fuel cell power generation device of the present invention is an operation method of a fuel cell power generation device including a power generation unit that generates power by using diluted fuel obtained by diluting the fuel to be diluted with water and air.
  • the operation method of the fuel cell power generator of the present invention can always provide the diluted fuel having the optimum concentration to the power generator of the fuel cell power generator without providing the concentration sensor or the like in the device.
  • the concentration of diluted fuel can be adjusted to maximize the output characteristics and power generation efficiency characteristics according to the load and the status of the fuel cell power generator.
  • the fuel cell power generator of the present invention uses diluted fuel obtained by diluting the fuel to be diluted with water and air.
  • the power generation unit that generates power the fuel supply unit that supplies the diluted fuel to the power generation unit at a predetermined flow rate, the voltage measurement unit that measures the output voltage of the power generation unit, and the concentration of the diluted fuel are adjusted.
  • the fuel cell device of the present invention can always supply diluted fuel having an optimal concentration to the power generation unit.
  • diluted fuel adjusted to the optimum concentration can be supplied to the power generation unit at all times. Characteristics can be supplied.
  • the operation method of the fuel cell power generation device of the present invention can always provide the diluted fuel having the optimum concentration to the power generation unit of the fuel cell power generation device without providing a concentration sensor or the like in the device. In other words, it is possible to operate without being affected by the effects of by-products or the deterioration of the sensor itself, which is a problem when adjusting the concentration using a concentration sensor. Then, the concentration of diluted fuel can be adjusted so that the output characteristics and power generation efficiency characteristics can be maximized according to the load and the state of the fuel cell power generator.
  • the fuel cell power generation device of the present invention can supply the diluted fuel always adjusted to the optimum concentration by the above-described operation method, and maximize the output characteristics and the power generation efficiency characteristics. be able to.
  • FIG. 1 is a configuration diagram of a fuel cell power generator according to the present invention.
  • FIG. 2 is a diagram showing an example of current-voltage characteristics and current output characteristics at a constant flow rate of the fuel cell power generator of the present invention.
  • FIG. 3 is a diagram showing an example of the relationship between the output voltage of the power generation unit and the flow rate to the power generation unit when the current density of the fuel cell power generation device of the present invention is constant.
  • FIG. 4 is a flowchart showing a method for operating the fuel cell power generator of the present invention.
  • the operation method of the fuel cell power generation device 1 of the present invention includes a power generation unit 2 that generates power by using a methanol aqueous solution of diluted fuel obtained by diluting methanol as a diluted fuel with water and air.
  • a power generation unit 2 that generates power by using a methanol aqueous solution of diluted fuel obtained by diluting methanol as a diluted fuel with water and air.
  • the fuel flow rate of the methanol aqueous solution supplied to the power generation unit 2 is increased or decreased, the output voltage of the power generation unit 2 is measured, and the fuel concentration of the methanol aqueous solution is optimized based on the relationship between the fuel flow rate and the output voltage. It is.
  • FIG. 1 is a configuration diagram showing an example of a fuel cell power generation device 1 operated by the operation method of the fuel cell power generation device 1 of the present invention.
  • the fuel cell power generation device 1 has a power generation unit 2 formed of an electrolyte membrane 20 sandwiched between a pair of electrodes including an anode 21 as a negative electrode and a force sword 22 as a positive electrode, and a methanol aqueous solution used for a power generation reaction.
  • the fuel mixing unit 30, the fuel supply unit 31 that supplies the methanol aqueous solution from the fuel mixing unit 30 to the power generation unit 2, and the methanol that is the diluted fuel diluted in the fuel mixing unit 30.
  • the power generation unit 2 includes a membrane-like electrolyte membrane 20 that allows protons to permeate, an anode 21 that has a catalyst in a power generation reaction, and a force sword 22, and the electrolyte membrane 20 is sandwiched between the anode 21 and the force sword 22 and bonded together. It is formed.
  • the electrolyte membrane 20 that allows protons to permeate is formed of a material that has both permeability, oxidation resistance, and heat resistance.
  • the anode 21 and the force sword 22 are made of a metal material, a carbon material, a conductive non-woven cloth, etc. For example, when a carbon material is used, a catalyst such as platinum is supported on the porous surface of the carbon material. You may let them.
  • the power generation unit 2 includes a voltage measurement unit 23 that can measure the output voltage from the power generation unit 2, and transmits the output voltage of the power generation unit 2 measured by the voltage measurement unit 23 to the control unit 44. can do.
  • the concentration of the aqueous methanol solution is adjusted by the fuel mixing unit 30 based on the measured output voltage and the flow rate of the aqueous methanol solution from the fuel supply unit 31.
  • the power generation unit 2 is a direct methanol fuel cell power generation device that uses methanol aqueous solution as a fuel and supplies it directly to the power generation unit 2.
  • the fuel cell power generation device 1 of the present invention is It can be changed as appropriate according to the power generation capacity of the fuel cell. Further, the power generation unit 2 may be provided with a temperature measuring device for measuring the temperature of the power generation unit 2. For example, the power generation unit 2 can be controlled so as not to be overheated due to heat generation of the power generation unit 2 due to a power generation reaction.
  • the fuel mixing unit 30 is connected to the diluted fuel storage unit 32 via a pump, a valve, and the like, and is connected to the power generation unit 2 via the fuel supply unit 31. Then, the fuel mixing section 30 stores the methanol to be diluted stored in the diluted fuel storage section 32 and the water storage section 42! From the water to generate a power generation reaction in the power generation section 2. It is possible to adjust the concentration of methanol aqueous solution, which is the diluted fuel necessary for the purpose. Then, the methanol aqueous solution whose concentration has been adjusted is supplied to the power generation unit 2 via the fuel supply unit 31 and used for the power generation reaction. In the fuel mixing unit 30, the concentration can be adjusted via the output voltage of the power generation unit 2 and the flow rate control unit 44 of the methanol aqueous solution from the fuel supply unit 31 to the power generation unit 2.
  • the fuel supply unit 31 is connected to the fuel mixing unit 30 and the power generation unit 2.
  • the fuel supply unit 31 can supply the methanol aqueous solution adjusted by the fuel mixing unit 30 to the anode 21 of the power generation unit 2 at a predetermined flow rate.
  • the flow rate of the aqueous methanol solution can be appropriately changed by the control unit 44.
  • the flow rate of the aqueous methanol solution is transmitted to the control unit 44 and becomes a parameter for adjusting the concentration of the aqueous methanol solution.
  • the concentration of the aqueous methanol solution can be adjusted in the fuel mixing unit 30 via the control unit 44 based on the flow rate of the aqueous methanol solution and the output voltage at the power generation unit 2.
  • the fuel supply unit 31 may use a valve, a pump, or the like instead of the fuel supply unit 31 as long as the flow rate of the aqueous methanol solution supplied to the power generation unit 2 can be controlled. It is changed appropriately according to.
  • a filter for removing impurities from the methanol aqueous solution supplied to the power generation unit 2 may be provided.
  • the diluted fuel storage unit 32 is connected to the fuel mixing unit 30 via a pump, a valve, or the like. Methanol, which is a diluted fuel to be supplied to the fuel mixing unit 30, is stored.
  • the fuel is supplied via a valve, a pump, etc. installed between the diluted fuel storage unit 32 and the fuel mixing unit 30. A necessary amount can be supplied to the mixing unit 30.
  • the gas-liquid separation unit 33 is connected to the power generation unit 2 and the fuel mixing unit 30.
  • the gas-liquid separation unit 33 can also separate the liquid component and the gas component from the discharged fuel force discharged from the anode 21 of the power generation unit 2.
  • the liquid component is supplied to the fuel mixing unit 30 through a pump, a filter, and the like, mixed with methanol and water, and again supplied as fuel to the anodic 21 of the power generation unit 2 through the fuel supply unit 31.
  • the gas component can be discharged outside the apparatus through the exhaust part 43.
  • the air supply unit 40 is connected to the power generation unit 2 and can supply air to the power sword 22 of the power generation unit 2.
  • the air supply unit 40 is not particularly limited as long as it can supply sufficient air for power generation reaction to the power sword 22 of the power generation unit 2, but examples thereof include a fan pump. .
  • the supplied air is used in the power generation reaction in the power generation unit 2.
  • the air supplied to the power generation unit 2 may include a filter for removing impurities and impurities.
  • the cooling unit 41 is connected to the power generation unit 2, the water storage unit 42, and the exhaust unit 43.
  • the cooling unit 41 can cool the air discharged from the power sword 22 of the power generation unit 2 and separate the water contained in the air discharged from the power generation unit 2.
  • the cooling unit 41 can supply the separated water to the water storage unit 42.
  • the gas component from which water has been separated is sent to the exhaust unit 43 and discharged together with the gas component discharged from the gas-liquid separation unit 33 to the outside of the apparatus.
  • the aerodynamic force discharged from the force sword 22 is also provided with a cooling unit 41 for separating water, but is not limited to this as long as water in the air can be separated.
  • a pump or the like may be provided to supply water to the water storage unit 42.
  • the water supplied to the water storage part 42 may be provided with a filter for removing impurities and impurities.
  • the water storage unit 42 is connected to the cooling unit 41 and the fuel mixing unit 30.
  • the water storage unit 42 stores the water separated by the cooling unit 41 and is useful for adjusting the aqueous methanol solution in the fuel mixing unit 30. Can be used.
  • the water stored in the water storage unit 42 can be supplied via a valve, a pump or the like according to the concentration of the methanol aqueous solution controlled by the fuel mixing unit 30.
  • the exhaust unit 43 is connected to the gas-liquid separation unit 33 and the cooling unit 41, and has an opening for discharging gas to the outside of the apparatus.
  • the exhaust unit 43 can exhaust the gas component discharged from the gas-liquid separation unit 33 and the gas component obtained by separating water from the air discharged from the force sword 22 in the cooling unit 41 to the outside of the apparatus.
  • the gas component discharged to the outside of the apparatus may be exhausted by burning a combustible compound contained in the gas component. Thereby, for example, it is possible to prevent by-products generated by the power generation reaction from being released to the outside of the apparatus.
  • the control unit 44 is configured to optimize the concentration of the methanol aqueous solution from the output voltage of the power generation unit 2 and the fuel flow rate of the methanol aqueous solution from the fuel supply unit 31 to the power generation unit 2.
  • the storage part 32 and the water storage part 42 can be controlled. For example, when increasing the concentration of the methanol aqueous solution from the output voltage and the fuel flow rate of the methanol aqueous solution, methanol is supplied from the diluted fuel storage unit 32 to the fuel mixing unit 30 via the control unit 44, and the fuel is mixed.
  • the concentration of the aqueous methanol solution can be increased at the mixing unit 30.
  • water when reducing the concentration of the aqueous methanol solution, water can be supplied from the water storage unit 42 to the fuel mixing unit 30, and the concentration of the aqueous methanol solution can be reduced in the fuel mixing unit 30.
  • the power generation unit 2 may be provided, or the optimum concentration of the methanol aqueous solution may be controlled from the temperature of the power generation unit 2 measured by the temperature measuring device.
  • the methanol aqueous solution is adjusted to a predetermined concentration by the control unit 44 in the fuel mixing unit 30.
  • the concentration adjustment at this time is adjusted by supplying methanol and water to the fuel mixing unit 30 from the diluted fuel storage unit 32 and the water storage unit 42.
  • the methanol aqueous solution adjusted by the fuel mixing unit 30 is supplied to the anode 21 of the power generation unit 2 through the fuel supply unit 31 at a predetermined flow rate.
  • air is supplied from the air supply unit 40 to the power sword 22 of the power generation unit 2.
  • the methanol aqueous solution is supplied to the anode 21 of the power generation unit 2 and the air is supplied to the cathode 22 of the power generation unit 2, whereby a power generation reaction can be caused in the power generation unit 2.
  • This power generation reaction is performed at the anode 21 with water and methanol in the methanol aqueous solution supplied.
  • Proton (H +) that passes through the electrolyte membrane 20 moves to the force sword 22.
  • the generated electrons (e_) move from the anode 21 to the force sword 22 through the external circuit.
  • the plugs and electrons that have moved, in the force sword 22, are supplied with oxygen in the supplied air and 3/20 + 6H +
  • the electric part 2 can perform a power generation reaction by supplying an aqueous methanol solution and air.
  • the aqueous methanol solution discharged from the anode 21 of the power generation unit 2 is supplied to the gas-liquid separation unit 33.
  • the discharged methanol aqueous solution can be gas-liquid separated.
  • gaseous components such as carbon dioxide generated by the power generation reaction in the power generation unit 2 mixed in the aqueous methanol solution can be separated.
  • a methanol aqueous solution, which is a liquid component from which the gas component has been separated, is supplied to the fuel mixing unit 30.
  • the fuel mixing unit 30 adjusts the concentration to be supplied to the power generation unit 2.
  • the air discharged from the power sword 22 of the power generation unit 2 is supplied to the cooling unit 41, and the cooling unit cools the air.
  • the separated water is supplied to the water storage unit 42.
  • the water stored in the water storage unit 42 is used for adjusting the concentration of the aqueous methanol solution in the fuel mixing unit 30.
  • the gas component such as carbon dioxide separated from the methanol aqueous solution by the gas-liquid separation unit 33 and the air separated from the water by the cooling unit 41 are supplied to the exhaust unit 43 and discharged to the outside of the apparatus. .
  • FIG. 2 is a diagram showing an example of current-voltage characteristics and current output characteristics of the fuel cell power generator at a constant flow rate.
  • the flow rate of methanol aqueous solution is constant, and lmol / U 0.6 mol Zl.
  • the change in current voltage characteristics and current output at each concentration of 0.4 molZl (molZl is expressed as M in the figure).
  • the fuel cell power generator is optimized so that the maximum output can be obtained with a 0.6 molZl aqueous methanol solution.
  • the air flow rate is constant.
  • the 0.6 molZl methanol solution which is the optimum concentration, has the maximum output voltage and output power at the same current density.
  • An ImolZl aqueous methanol solution with a higher concentration than the 6molZl aqueous methanol solution has a lower output voltage than the 0.6molZl aqueous methanol solution when compared at a given output current. And only output power can be obtained. This is due to the phenomenon that the methanol solution in the methanol solution supplied to the anode of the power generation section passes through the methanol power electrolyte and moves to the power sword (V, so-called crossover), and the current-voltage characteristics and current output characteristics deteriorate. It is because it ends.
  • a 0.4 molZl aqueous methanol solution having a lower concentration than the 0.6 molZl aqueous methanol solution can provide only lower output voltage and output power than the 0.6 molZl aqueous methanol solution when compared at a given output current. Absent. This is because methanol is insufficient and current-voltage characteristics and current output characteristics deteriorate. Therefore, it can be seen that in order to perform an optimal power generation reaction, it is necessary to supply a methanol aqueous solution having an optimal concentration to the power generation unit.
  • the optimal concentration of the methanol aqueous solution in the fuel cell power plant that has not yet been operated may differ from the optimal concentration of the methanol aqueous solution in the fuel cell power plant after a predetermined operating time. To do this, it is necessary to flexibly change the concentration of the aqueous methanol solution.
  • FIG. 3 is a diagram showing an example of the relationship between the output voltage of the power generation unit and the flow rate to the power generation unit under a constant current density. For example, each of lmol / U 0.6 molZl and 0.4 molZl It shows the change of output voltage with concentration. At this time, the air flow rate is constant.
  • the fuel cell power generator having the characteristics shown in FIG. 3 is configured so as to be steadily operated with a methanol aqueous solution flow rate of 20 cc Zmin. For example, as in Fig. 2, when the power generation unit is optimized at 0.6 molZl, the output voltage does not change at 20 ccZmin at 0.6 molZl.
  • the methanol solution of ImolZl which is higher than the optimal concentration, shows that the output voltage decreases as the flow rate is increased.
  • the 0.4 molZl aqueous methanol solution which is lower than the optimum concentration, it can be seen that the output voltage increases as the flow rate is increased.
  • the operation method of the fuel cell power generator of the present invention utilizes the relationship between the voltage and the flow rate in the difference in the concentration of the methanol aqueous solution. If the output voltage does not change as the flow rate of the aqueous methanol solution is increased, this indicates that the concentration of the aqueous methanol solution has been optimized. In addition, if the output voltage is reduced by increasing the flow rate of the aqueous methanol solution, It shows that the concentration of the aqueous anol solution is higher than the optimum concentration. Further, when the output voltage is increased by increasing the flow rate of the aqueous methanol solution, the concentration of the aqueous methanol solution is lower than the optimum concentration.
  • the concentration of the aqueous methanol solution is adjusted so as to reduce the concentration of the aqueous methanol solution, whereby an aqueous methanol solution having an optimal concentration can be obtained.
  • the methanol aqueous solution having the optimum concentration can be obtained by adjusting the concentration so that the concentration of the methanol aqueous solution is increased.
  • the concentration of the aqueous methanol solution can be adjusted even when the flow rate is reduced. For example, if the output voltage is reduced by reducing the flow rate of the aqueous methanol solution, the concentration of the aqueous methanol solution is lower than the optimum concentration. Therefore, by adjusting the concentration so that the concentration of the methanol aqueous solution is increased, an aqueous methanol solution with an optimal concentration can be obtained. On the other hand, when the output voltage is increased by reducing the flow rate of the aqueous methanol solution, the concentration of the aqueous methanol solution is higher than the optimum concentration. Therefore, by adjusting the concentration so as to reduce the concentration of the aqueous methanol solution, an aqueous methanol solution having an optimal concentration can be obtained.
  • the aqueous methanol solution can be optimized without using a concentration sensor or the like that measures the concentration of the aqueous methanol solution supplied to the power generation unit. Even if the current-voltage characteristics and the current output characteristics change due to deterioration of the electrolyte, etc., the concentration of the aqueous methanol solution can be adjusted so that the maximum output is obtained at that time by the output of the power generation unit.
  • FIG. 4 is a flowchart showing a method for operating the fuel cell power generator of the present invention.
  • the methanol aqueous solution and the air are supplied to the power generation unit upon activation, and the power generation reaction proceeds as described above.
  • the fuel cell power generator is started, as shown in step S1, the output voltage is measured by the voltage measurement unit of the power generation unit, and the measured value is transmitted to the control unit, and the change of the output voltage is monitored by the control unit. Is done. At this time, the current density of the power generation unit is kept constant.
  • step S2 if there is no drop in the output voltage monitored by the control unit, the process returns to step S1, and the output voltage of the power generation unit continues to pass through the voltage measurement unit. Monitored at. [0046]
  • step S3 when a decrease in the output voltage of the power generation unit is confirmed by the control unit, the process of step S3 is performed. If a decrease in the output voltage of the power generation unit is observed, this indicates that the methanol aqueous solution having the optimum concentration in the power generation unit has been supplied. Therefore, it is necessary to adjust the aqueous methanol solution supplied to the power generation unit to an optimum concentration. As shown in Fig.
  • step S3 control is performed so that the fuel flow rate is increased in the fuel supply unit via the control unit.
  • step S4 the output voltage measured by the voltage measurement unit of the power generation unit is confirmed, and the output voltage monitored in step S1 is compared with the control unit. If the return of the output voltage is not confirmed by the control unit, in step S8, the control unit controls the fuel supply unit to return the fuel flow increased in step S3 to the original flow rate.
  • the fuel mixing unit is controlled through the control unit so as to reduce the concentration of the methanol aqueous solution.
  • step S5 the control unit controls the fuel supply unit so as to return the fuel flow rate increased in step S3 to the original flow rate, as in step S6.
  • the fuel mixing unit is controlled through the control unit so as to increase the concentration of the aqueous methanol solution.
  • step S6 the concentration of the methanol aqueous solution is increased, and the output voltage measured by the voltage measurement unit of the power generation unit is compared with the output voltage monitored in step S1 again by the control unit. Then, as shown in step S7, if the return of the output voltage is not confirmed by the control unit, it indicates that the concentration of the aqueous methanol solution is still low, so the flow returns to step S6 to further increase the concentration of the aqueous methanol solution.
  • the fuel supply unit is controlled via the control unit.
  • the control unit confirms that the output voltage has been restored, it indicates that the concentration of the methanol aqueous solution has reached the optimum concentration, and proceeds to step S11 to complete the concentration adjustment.
  • step S9 the concentration of the aqueous methanol solution is decreased, and the output voltage measured again by the voltage measuring unit of the power generation unit is compared with the output voltage monitored in step S1 by the control unit. Then, as shown in step S10, if the return of the output voltage is not confirmed by the control unit, it indicates that the concentration of the methanol aqueous solution is still high, so that the procedure returns to step S9 to further reduce the concentration of the methanol aqueous solution.
  • the fuel supply unit is controlled via the control unit. If the return of the output voltage is confirmed by the control unit, it indicates that the concentration of the aqueous methanol solution has become the optimum concentration, moves to step S11, and the concentration adjustment ends.
  • the adjustment of the methanol aqueous solution is not limited to the determination based on the increase in the fuel flow rate, but the output voltage increases when the fuel flow rate is decreased at a higher concentration than the optimal concentration methanol aqueous solution, The same judgment can be made by reducing the fuel flow rate within the range of the fuel flow rate that shows a tendency for the output voltage to decrease when the fuel flow rate is reduced at a lower concentration than the optimum concentration of aqueous methanol solution.
  • step S11 When power generation is continued as in step S11, the process returns to step S1, and monitoring of the output voltage measured by the voltage measurement unit of the power generation unit is continued in the control unit. On the other hand, when the operation of the fuel cell power generation device is stopped by this, the fuel supply unit is stopped via the control unit, and the operation of the device is stopped.
  • the concentration of the aqueous methanol solution necessary for maximizing the output characteristics and power generation efficiency characteristics of the fuel cell power generation device without performing a complicated calculation. Since the concentration is adjusted based on the output voltage of the power generation unit, for example, even when the output voltage decreases due to aging deterioration of the fuel cell power generation device, the same operation is performed to obtain the optimum methanol at that time.
  • the concentration of the aqueous solution can be adjusted. That is, it is possible to flexibly adjust the methanol aqueous solution to an optimal concentration more flexibly than measuring the absolute methanol aqueous solution by a sensor, calculation or the like and adjusting the concentration so that it becomes a predetermined value.
  • the control may be performed by increasing or decreasing the output voltage.
  • the control unit determines whether the output voltage increases or decreases. If the output voltage increases, return the fuel flow to the original, methanol Since the concentration of the aqueous solution is low, the fuel mixing unit is controlled via the control unit so as to increase the concentration. This is continued until the output begins to drop. On the other hand, when the output voltage decreases, the fuel flow rate is restored, and the concentration of the methanol aqueous solution is high.
  • the fuel mixing unit is controlled via the control unit so as to decrease the concentration. This is continued until the output voltage starts to rise.
  • the aqueous methanol solution can always be adjusted to the optimum concentration, and the fuel cell power generator can always be operated at the maximum output voltage.
  • the control unit may confirm the voltage value required for the load, and the concentration of the aqueous methanol solution may be adjusted so as to output the voltage corresponding to the voltage value.
  • the concentration of aqueous methanol solution is 0.6 mol / l and the flow rate is optimized at 20 ccZmin, the output voltage is lower at 0.4 molZl even at the same flow rate.
  • the concentration of the methanol aqueous solution can be reduced to control the output voltage to meet the required voltage.
  • the fuel cell power generator can be operated at an output voltage commensurate with the load, and efficient operation can be performed.
  • a table that shows the relationship between the flow rate of the aqueous methanol solution and the output voltage as shown in FIG. 3 may be provided in the control unit of the fuel cell power generator. For example, if the flow rate of the methanol aqueous solution is changed, the tendency of the change in the output voltage is compared with the table provided in the control unit, and if the output voltage decreases as the flow rate increases, the concentration of the methanol aqueous solution If the output voltage increases as the flow rate increases, the concentration of the aqueous methanol solution may be controlled to increase the concentration of the aqueous methanol solution.
  • an aqueous methanol solution having an optimal concentration can be supplied to the power generation unit at the time of measurement.
  • the table provided in the control unit may be rewritten. This facilitates the determination by the control unit.
  • the concentration of the aqueous methanol solution can be adjusted more efficiently by providing such a table.
  • concentration of the aqueous methanol solution can be adjusted so that the output characteristics and power generation efficiency characteristics can be maximized according to the load and the state of the fuel cell power generation device.
  • the fuel cell power generation device of the present invention maintains a constant power density output from the power generation unit that generates power using diluted fuel obtained by diluting the fuel to be diluted with water and air, and the power generation unit. And a fuel mixing section for adjusting the concentration of the diluted fuel by increasing or decreasing the flow rate of the diluted fuel supplied to the power generation section and measuring the output voltage of the power generation section.
  • the fuel cell power generation device of the present invention includes a power generation unit that generates power using a methanol aqueous solution that is a diluted fuel and air, and a fuel supply that supplies the methanol aqueous solution to the power generation unit at a predetermined speed.
  • a fuel mixing unit that adjusts the methanol aqueous solution to a predetermined concentration, and whether to increase or decrease the concentration of the methanol aqueous solution in the fuel mixing unit from the output voltage of the power generation unit and the flow rate of the methanol aqueous solution from the fuel supply unit. It has a control unit to judge. Then, the concentration of the aqueous methanol solution is adjusted by a control method as shown in FIG.
  • the fuel cell power generator 1 of the present invention can always supply the methanol aqueous solution with the optimum concentration to the power generator 2.
  • the diluted fuel adjusted to the optimum concentration can be supplied to the power generation unit 2 at all times. By supplying power generation efficiency characteristics wear.
  • the methanol to be diluted used in the present embodiment is not limited to this, and it is also possible to use a fuel used in a normal fuel cell.
  • a fuel used in a normal fuel cell For example, ethanol or dimethyl ether can be used.
  • a current measurement unit that can measure the output current is provided in the power generation unit, and the fuel cell power generation device of the present invention can be operated with reference to the output current. it can.

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Abstract

L’invention porte sur un procédé d’entraînement d’équipement de production d’énergie à pile à combustible susceptible d’injecter un combustible dilué d’une concentration optimale dans une pièce de production d’énergie sans devoir réaliser de mesure de concentration absolue à l’aide d’un capteur ou équivalent. L’invention concerne un équipement de production d’énergie à pile à combustible excité par ce procédé d’entraînement. Le changement de tension de sortie de la pièce de production d’énergie s’observe conformément au débit de combustible du combustible dilué, où le combustible dilué pouvant ainsi toujours être ajusté pour présenter une concentration optimale, sans devoir réaliser de mesure de concentration absolue à l’aide d’un capteur ou équivalent. De plus, ce procédé d’entraînement peut présenter la caractéristique d’énergie la plus efficace et l’efficacité de production d’énergie la plus grande conformément au statut d’une charge et à celui de l’équipement de production d’énergie à pile à combustible.
PCT/JP2005/016133 2004-09-06 2005-09-02 Procédé d’entraînement d’équipement de production d’énergie à pile à combustible et équipement de production d’énergie à pile à combustible WO2006028021A1 (fr)

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US11/574,791 US8241799B2 (en) 2004-09-06 2005-09-02 Methods of operating fuel cell power generators, and fuel cell power generators
EP05781399A EP1798796B1 (fr) 2004-09-06 2005-09-02 Procédé d entraînement d équipement de production d énergie à pile à combustible et équipement de production d énergie à pile à combustible

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JP2004-259044 2004-09-06
JP2004259044A JP4924786B2 (ja) 2004-09-06 2004-09-06 燃料電池発電装置の運転方法及び燃料電池発電装置

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JP2009054546A (ja) 2007-08-29 2009-03-12 Toshiba Corp 燃料電池装置の駆動方法
KR20090043966A (ko) * 2007-10-30 2009-05-07 삼성에스디아이 주식회사 직접액체 연료전지 및 그것의 연료농도 제어 방법 및 장치
JP5268832B2 (ja) 2009-08-31 2013-08-21 株式会社日立製作所 有機系燃料を用いた燃料電池
JP5556123B2 (ja) * 2009-10-29 2014-07-23 株式会社村田製作所 燃料電池システム
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ITVR20110109A1 (it) 2011-05-19 2012-11-20 Stefano Cavalli Metodo di controllo e massimizzazione dell?efficienza elettrica e della produzione di potenza di una pila a combustibile - method of controlling and maximizing the electric efficiency and the power output of a fuel cell
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JP2006073486A (ja) 2006-03-16
CN100481596C (zh) 2009-04-22
EP1798796B1 (fr) 2011-08-17
EP1798796A4 (fr) 2007-11-14
US20070218323A1 (en) 2007-09-20
JP4924786B2 (ja) 2012-04-25
EP1798796A1 (fr) 2007-06-20
US8241799B2 (en) 2012-08-14

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